51V NMR Studies of Crystalline Divalent Metal Vanadates and Divanadates

• Satoshi Hayakawa

  Institute for Chemical Research, Kyoto UniversityUji, Kyoto 611

• Toshinobu Yoko

  Institute for Chemical Research, Kyoto UniversityUji, Kyoto 611

• Sumio Sakka

  Institute for Chemical Research, Kyoto UniversityUji, Kyoto 611

抄録

51V static and magic-angle spinning (MAS) NMR spectra of crystalline divalent metal vanadates, M3(VO4)2 (M = Mg, Sr, Ba, Zn, Pb) and Mg2M′(VO4)2 (M′ = Sr, Ba, Pb) and divanadates, M2V2O7 (M = Mg, Ca, Sr, Ba, Zn, Pb) have been measured. In vanadates and dichromate-type divanadates, the 51V isotropic chemical shifts decrease linearly with decreasing electronegativity of divalent metal atom adjacent to the VO4-tetrahedron. This was interpreted by considering that the electron density and the symmetry of VO4-tetrahedron increases with decreasing electronegativity of divalent metal atom. This effect was more significant in vanadates than in divanadates. In divanadates the isotropic chemical shifts of the thortveitite-type configuration appeared at lower frequencies than that of the dichromate-type configuration. This was explained by assuming that the degree of s-hybridization of the oxygen orbitals in the V–O–V bonds is higher in the thortveitite-type than in the dichromate-type.

収録刊行物

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 66 (11), 3393-3400, 1993-11-01

  Oxford University Press (OUP)

キーワード

• General Chemistry

詳細情報

• CRID: 1360565169057351552
• NII論文ID: 130004148105
• DOI: 10.1246/bcsj.66.3393
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/66/11/3393/56218264/bcsj.66.3393.pdf
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